Method of Manufacturing Integrated Circuit Device

This application is based on and claims priority under 35 U.S.C. § 119 to Korean Patent Application No. 10-2024-0148965, filed on Oct. 28, 2024, in the Korean Intellectual Property Office, the disclosure of which is incorporated by reference herein in its entirety.

The inventive concepts relate to methods of manufacturing an integrated circuit device, and more particularly, to methods of manufacturing an integrated circuit device utilizing a multi-patterning technique.

With the rapid development of the electronics industry and the growing demands of users, electronic devices have been miniaturized while achieving higher performance, and thus, the downscaling of integrated circuit devices included in electronic devices has progressed rapidly. Accordingly, multi-patterning technologies, such as Double Patterning Technology (DPT) and Quadruple Patterning Technology (QPT), have been introduced to manufacture integrated circuit devices.

The inventive concepts provide methods of manufacturing an integrated circuit device capable of forming patterns with improved uniformity.

According to an example embodiment of the inventive concepts, a method of manufacturing an integrated circuit device may include forming a mandrel pattern on a base layer, the mandrel pattern having a stack structure that includes a mandrel base pattern and a mandrel hard mask pattern, attaching precursor inhibitors to a surface of the base layer and a surface of the mandrel hard mask pattern, forming a side surface spacer layer on a side surface of the mandrel base pattern, removing a first portion of the precursor inhibitors, leaving a second portion of the precursor inhibitors between the base layer and the side surface spacer layer, forming a spacer bonding layer by modifying the second portion of the precursor inhibitors to bond the base layer to the side surface spacer layer, and then forming a spacer pattern with a stack structure including the spacer bonding layer and the side surface spacer layer, removing the mandrel pattern, and forming a base pattern by patterning the base layer by using the spacer pattern as an etch mask.

According to an example embodiment of the inventive concepts, a method of manufacturing an integrated circuit device may include forming a mandrel pattern on a base layer, the mandrel pattern having a stack structure that includes a mandrel base pattern and a mandrel hard mask pattern, exposing a surface of the base layer and a surface of the mandrel hard mask pattern to precursor inhibitors such that the precursor inhibitors are not attached to a surface of the mandrel base pattern but a first ligand of each of the precursor inhibitors is attached to the surface of the base layer and the surface of the mandrel hard mask pattern, the precursor inhibitors each including a central element, the first ligand that is a bonding moiety bonded to the central element, and a second ligand that is an inhibition moiety, forming a side surface spacer layer on a side surface of the mandrel base pattern, among the precursor inhibitors, leaving a first portion of the precursor inhibitors attached to a portion of the surface of the base layer between the base layer and the side surface spacer layer and removing the second portion of the precursor inhibitors attached to another portion of the surface of the base layer and the surface of the mandrel hard mask pattern, forming a spacer bonding layer by modifying the first portion of the precursor inhibitors to bond the base layer to the side surface spacer layer, and then forming a spacer pattern with a stack structure including the spacer bonding layer and the side surface spacer layer, removing the mandrel pattern, and forming a base pattern by patterning the base layer by using the spacer pattern as an etch mask.

2 3 2 2 2 2 According to an example embodiment of the inventive concepts, a method of manufacturing an integrated circuit device may include forming a mandrel pattern on a base layer, the mandrel pattern having a stack structure that includes a mandrel base pattern and a mandrel hard mask pattern, performing surface treatment with hydrogen radicals to make each of a surface of the base layer and a surface of the mandrel hard mask pattern hydrophilic and a surface of the mandrel base pattern hydrophobic, exposing the surface of the base layer and the surface of the mandrel hard mask pattern to precursor inhibitors such that the precursor inhibitors are attached to the surface of the base layer and the surface of the mandrel hard mask pattern through a first ligand of each of the precursor inhibitors, the precursor inhibitors each including a central element, the first ligand functioning as a bonding moiety bonded to the central element, and a second ligand functioning as an inhibition moiety, performing a preprocessing process of flowing HO onto the base layer and the mandrel pattern, forming a side surface spacer layer on a side surface of the mandrel base pattern of the mandrel pattern by using a reactant that does not react with the precursor inhibitors and a spacer deposition precursor that reacts with the reactant, such that the side surface spacer layer and the base layer are spaced apart from each other with the precursor inhibitors therebetween, among the precursor inhibitors, leaving a first portion of the precursor inhibitors attached to portions of the surface of the base layer between the base layer and the side surface spacer layer and removing a second portion of the precursor inhibitors attached to other portions of the surface of the base layer and the surface of the mandrel hard mask pattern, forming a spacer bonding layer, which bonds the base layer to the side surface spacer layer, by changing the first portion of the precursor inhibitors due to ozone (O) or plasma containing oxygen radicals (O, HO, NO, CO, or NO) and forming a spacer pattern with a stack structure including the spacer bonding layer and the side surface spacer layer, removing the mandrel pattern, and forming a base pattern by patterning the base layer by using the spacer pattern as an etch mask.

1 FIG. is a flowchart of a method of manufacturing an integrated circuit device, according to an example embodiment.

1 FIG. 110 Referring to, in operation S, a mandrel pattern is formed on a base layer. The mandrel pattern may be formed to have a stack structure including a mandrel base pattern and a mandrel hard mask pattern. In some example embodiments, for example, the surface of the base layer, the surface of the mandrel base pattern, and the surface of the mandrel hard mask pattern may each be hydrophilic.

120 In operation S, after the mandrel pattern is formed, surface treatment is performed on the base layer and the mandrel pattern. For example, through hydrogen (H) radial treatment, the surface of the mandrel base pattern may be reduced to become hydrophobic, and each of the surfaces of the base layer and the mandrel hard mask pattern may remain hydrophilic.

130 In operation S, the surface of the base layer and the surface of the mandrel pattern are exposed to precursor inhibitors (PIs) such that the PIs are attached to the surfaces of the base layer and the mandrel hard mask pattern of the mandrel pattern. The PIs may be attached to the surfaces of the base layer and the mandrel hard mask pattern, both of which are hydrophilic, and may not be attached to the surface of the mandrel base pattern, which is hydrophobic.

140 In operation S, a side surface spacer layer is formed on side surfaces of the mandrel pattern. The side surface spacer layer may be formed only on the surface of the mandrel base pattern but may not be formed on the surface of the base layer and the surface of the mandrel hard mask pattern.

150 In operation S, a spacer bonding layer for bonding the base layer to the side surface spacer layer is formed, and a spacer pattern with a stack structure of the spacer bonding layer and the side surface spacer layer is formed. The spacer bonding layer may be formed by modifying the PIs. The spacer bonding layer may be between the upper surface of the base layer and the lower surface of the side surface spacer layer and bond the base layer to the side surface spacer layer.

160 170 In operation S, the mandrel pattern is removed, leaving the spacer pattern on the base layer. Then, in operation S, the base layer is patterned using the spacer pattern as an etch mask, thereby forming a base pattern. In some example embodiments, a target layer located on the lower portion of the base pattern may be patterned using the base pattern as an etch mask, thereby forming a target pattern.

2 2 FIGS.A andB are conceptual views of integrated circuit devices manufactured according to a method of manufacturing an integrated circuit device, according to some example embodiments.

2 FIG.A 1000 1010 1020 1010 Referring to, an integrated circuit deviceaccording to an example embodiment may include a memory cell array regionand a peripheral circuit regionaround the memory cell array region.

1010 A memory device may be arranged in the memory cell array region. The memory device may be, for example, Static Random Access Memory (SRAM), Dynamic RAM (DRAM), Magnetic RAM (MRAM), Phase change RAM (PRAM), Resistive RAM (RRAM), Ferroelectric RAM (FeRAM), flash memory, or the like, but example embodiments are not limited thereto.

1020 1010 In the peripheral circuit region, circuit devices configured to operate the memory device in the memory cell array regionmay be arranged. The circuit device may be, for example, a read circuit, a write circuit, or the like, but example embodiments are not limited thereto.

1010 1020 1010 1020 According to some example embodiments, patterns, which are arranged in the memory cell array regionand/or the peripheral circuit region, may be formed. For example, at least some of active regions, conductive line patterns, hole patterns, and other configurations arranged in the memory cell array regionand/or the peripheral circuit regionmay be formed.

2 FIG.B 1100 1110 1120 1110 1120 1100 1110 Referring to, an integrated circuit deviceaccording to an example embodiment may include a logic regionand an SRAM region. Here, the logic regionand the SRAM regionare merely examples. Example embodiments are not limited thereto. The integrated circuit devicemay include the logic regionand a region where other memory devices are formed (e.g., a region where DRAM, MRAM, PRAM, RRAM, flash memory, and the like are formed).

1110 The logic regionmay be a region where a semiconductor device including various types of individual devices is formed. The individual devices may include various microelectronic devices, for example, a metal-oxide-semiconductor field effect transistor (MOSFET) such as a complementary metal-insulator-semiconductor (CMOS) transistor, an image sensor such as system large scale integration (LSI) or a CMOS imaging sensor (CIS), a micro-electro-mechanical system (MEMS), active elements, passive elements, and/or the like.

1110 1120 1110 1120 According to some example embodiments, patterns arranged in the logic regionand/or the SRAM regionmay be formed. For example, at least some of active regions, conductive line patterns, hole patterns, and other configurations arranged in the logic regionand/or the SRAM regionmay be formed.

3 3 FIGS.A toK are cross-sectional views illustrating a method of manufacturing an integrated circuit device, according to an example embodiment.

3 FIG.A 110 200 300 100 Referring to, a target layer, a base layer, and a preliminary mandrel layerare sequentially formed on a substrate.

100 100 100 The substratemay include a semiconductor substrate. In some example embodiments, the semiconductor substrate may include semiconductor materials such as group IV semiconductor materials, group III-V semiconductor materials, group II-VI semiconductor materials, or II-VI oxide semiconductor materials. The group IV semiconductor material may include, for example, silicon (Si), germanium (Ge), or Si—Ge. The group III-V semiconductor material may include, for example, gallium arsenide (GaAs), indium phosphide (InP), gallium phosphide (GaP), indium arsenide (InAs), indium antimonide (InSb), or indium gallium arsenide (InGaAs). The group II-VI semiconductor material may include, for example, zinc telluride (ZnTe) or cadmium sulfide (Cds). The substratemay be supplied as a bulk wafer or an epitaxial layer. In some example embodiments, the substratemay include a silicon-on-insulator (SOI) substrate or a germanium-on-insulator (GeOI) substrate.

110 110 110 110 100 110 100 110 110 110 110 The target layermay include a semiconductor material, a conductive material, or an insulating material. In some example embodiments, the target layermay include a semiconductor material, and portions of the target layermay become active regions. For example, the target layermay be an upper portion of the substrate. For example, the target layermay be a semiconductor material layer formed on the substrateby epitaxy. In some example embodiments, the target layermay include a conductive material, and portions of the target layermay become conductive lines. In some example embodiments, the target layermay include an insulating material, and portions of the target layerare removed. and thus, holes may be formed.

200 110 110 200 110 200 200 2 The base layermay include a material having etch selectivity relative to the target layer. For example, when the target layerincludes a conductive material or an insulating material, the base layermay include a semiconductor material such as Si. For example, when the target layerincludes a semiconductor material such as Si, the base layermay include an insulating material that contains Si elements such as silicon oxynitride (SiON) or silicon oxide (SiO). The base layeralso may be referred to as a hard mask layer.

300 200 300 300 310 320 320 310 310 320 310 320 320 310 320 200 320 2 At least some portions of the preliminary mandrel layermay include a material having etch selectivity relative to the base layer. For example, at least some portions of the preliminary mandrel layermay include a material that contains carbon (C). The preliminary mandrel layermay have a stack structure including a mandrel base layerand a mandrel hard mask layer. The mandrel hard mask layermay have a thickness less than that of the mandrel base layer. The mandrel base layerand the mandrel hard mask layermay include different materials. In some example embodiments, the mandrel base layermay include a material containing C, and the mandrel hard mask layermay include a material that does not contain C. For example, the mandrel hard mask layermay include a material that does not contain C but contains Si elements. In some example embodiments, the mandrel base layermay include an Amorphous Carbon Layer (ACL) or a Carbon-based Spin On Hardmask (C-SOH). In some example embodiments, each of the mandrel hard mask layerand the base layermay include a material that does not contain C but contains Si elements. For example, the mandrel hard mask layermay include an insulating material such as SiON or SiO.

3 3 FIGS.A andB 300 300 300 310 310 320 320 300 300 300 300 Referring totogether, the preliminary mandrel layeris patterned to form a plurality of mandrel patternsP. Each of the mandrel patternsP may have a stack structure that includes a mandrel base patternP, which is a portion of the mandrel base layer, and a mandrel hard mask patternP, which is a portion of the mandrel hard mask layer. In some example embodiments, the mandrel patternsP may be formed by patterning the preliminary mandrel layerthrough Extreme Ultraviolet (EUV) Lithography. In some example embodiments, the mandrel patternsP may be formed by patterning the preliminary mandrel layerby using a plurality of hard mask patterns as etch masks, wherein the hard mask patterns are formed by multi-patterning technologies such as Double Patterning Technology (DPT).

200 310 320 In some example embodiments, the surfaces of the base layer, the mandrel base patternP, and the mandrel hard mask patternP may each be hydrophilic.

3 FIG.C 200 300 350 350 200 320 300 350 310 310 200 320 350 200 320 310 Referring to, the base layerand the mandrel patternsP are exposed to the PIssuch that the PIsare attached to the surface of the base layerand the surface of the mandrel hard mask patternP of each mandrel patternP. In some example embodiments, before being exposed to the PIs, the surface of the mandrel base patternP may be reduced to become hydrophobic. For example, the oxidized surface of the mandrel base patternP may be reduced to become hydrophobic through surface treatment using H radicals. Each of the surface of the base layerand the surface of the mandrel hard mask patternP may remain hydrophilic. The PIsmay be attached to the surface of the base layerand the surface of the mandrel hard mask patternP, both of which are hydrophilic, and may not be attached to the surface of the mandrel base patternP that is hydrophobic.

350 350 352 354 352 356 352 352 354 356 354 356 354 352 350 352 350 352 350 356 3 5 3 2 3 2 3 For example, the PImay be an organo-metallic precursor that includes a moiety capable of suppressing chemical bonding. The PIincludes a central element, a first ligandbonded to the central element, and a second ligand. In some example embodiments, the central elementmay be at least one metal element containing metal atoms, metallic ions, metal compounds, metal alloys, or any combination thereof. For example, the central elementmay be titanium (Ti), zirconium (Zr), or hafnium (Hf). The first ligandmay be referred to as the bonding moiety, and the second ligandmay be referred to as the inhibition moiety. In some example embodiments, the first ligandmay be an alkoxy ligand, and the second ligandmay be a cyclopentadienyl-ligand, but example embodiments are not limited thereto. For example, the first ligandmay be a methoxy (—OCH3) ligand. For example, when the central elementincludes Ti, the PImay be trimethoxy-(pentamethylcyclopentadienyl)-titanium, Cp(CH)Ti(OMe)(TMPMCT), but is not limited thereto. For example, when the central elementincludes Zr, the PImay be cyclopentadienyl tris(dimethylamino) zirconium, CpZr(NMe)(CpTDMAZ), but is not limited thereto. For example, when the central elementincludes Hf, the PImay be cyclopentadienyl tris(dimethylamino) hafnium, CpHf(NMe)(CPTDMAH), but is not limited thereto. The second ligandmay have a structure, for example, a linear carbon chain or an aromatic ring, which is chemically stable and has a specific length and area, thus inhibiting reactions occurring between the precursor and the surface. The abbreviation “Me” refers to a methyl group, “Et” to an ethyl group, “Cp” to cyclopentadienyl, “Pr” to a propyl group, “iPr” to an isopropyl group, “Bu” to a butyl group, “tBu” to a tert-butyl group (1,1-dimethylethyl), and “thd” to 2,2,6,6-tetramethyl heptanedionate.

354 350 200 320 354 350 200 320 310 350 200 320 350 350 200 320 354 350 200 320 The first ligandsof the PIsmay be attached to the surfaces of the base layerand the mandrel hard mask patternP. For example, the first ligandsof the PIsmay be attached to the surfaces of the base layerand the mandrel hard mask patternP, both of which are hydrophilic, but may not be attached to the surface of the mandrel base patternP that is hydrophobic. The PIsmay be attached to the surfaces of the base layerand the mandrel hard mask patternP as a monolayer. For example, other PIsmay not be attached to the PIsalready attached to the surfaces of the base layerand the mandrel hard mask patternP. In some example embodiments, at least some of the first ligandsin some of the PIsmay be converted to OH and thus may chemically bond with the base layerand/or the mandrel hard mask patternP.

3 FIG.D 360 310 360 360 360 360 350 360 360 350 360 350 360 360 200 300 360 356 350 350 360 360 2 2 2 2 4 4 4 3 2 3 2 Referring to, the side surface spacer layeris formed on the surface of the mandrel base patternP. The side surface spacer layermay include an insulating material that includes oxide, nitride, or metal oxide. For example, the side surface spacer layermay include titanium oxide (TiO), hafnium oxide (HfO), zirconium oxide (ZrO), silicon oxide (SiO), or silicon nitride (SiN). In some example embodiments, when the side surface spacer layerincludes metal oxide, the metal elements included in the side surface spacer layermay be the same as the central elements of the PIs. However, example embodiments are not limited thereto. For example, when the side surface spacer layerincludes metal oxide, the metal elements in the side surface spacer layermay be different from the central elements of the PIs. In some example embodiments, when the side surface spacer layerincludes an insulating material instead of metal oxide, the central elements of the PIsmay be different from the elements in the side surface spacer layer. The side surface spacer layermay be formed by injecting a spacer deposition precursor and a reactant onto the base layerand the mandrel patternsP. In some example embodiments, the side surface spacer layermay be formed by performing Atomic Layer Deposition (ALD) using the spacer deposition precursor. For example, the spacer deposition precursor may include tetrakis dimethylamino titanium (TDMAT), titanium tetrachloride (TiCl), tetrakis dimethylamido hafnium (TDMAHf), HfCl, tetrakis dimethylamido zirconium (TDMAZr), ZrCl, chlorosilanes, aminosilanes, silvamines, or silanes. The reactant is limited to a gas, which does not react with the second ligandsof the Pisbut reacts with the spacer deposition precursor, to reduce or prevent the deposition reaction in the area including the PIs. For example, in the process of forming the side surface spacer layer, plasma that contains Oor O and provides highly reactive O radicals is excluded, and HO reacting with the spacer deposition precursor may be used as the reactant. In other words, in the process of forming the side surface spacer layer, instead of plasma containing Oor O and providing highly reactive O radicals, HO reacting with the spacer deposition precursor may be used as the reactant.

360 310 200 320 360 310 350 200 320 350 200 360 350 The side surface spacer layermay be formed only on the surface of the mandrel base patternP, but may not be formed on the surfaces of the base layerand the mandrel hard mask patternP. For example, the side surface spacer layermay be formed on the surface of the mandrel base patternP to which the PIsare not attached, but may not be formed on the surfaces of the base layerand the mandrel hard mask patternP to which the PIsare attached. For example, the upper surface of the base layerand the lower surface of the side surface spacer layermay be spaced apart from each other with the PIstherebetween.

360 200 300 360 200 300 200 300 310 360 200 300 354 356 350 350 200 354 354 200 350 200 2 2 2 2 3 2 In some example embodiments, before the side surface spacer layeris formed, a preprocessing process of flowing HO onto the base layerand the mandrel patternsP may be performed. In some example embodiments, to form the side surface spacer layer, HO may also be injected along with the spacer deposition precursors onto the base layerand the mandrel patternsP. When HO is supplied onto the base layerand the mandrel patternsP, the surface of the mandrel base patternP becomes hydrophilic, and thus, the growth rate of the side surface spacer layermay increase. When HO is supplied onto the base layerand the mandrel patternsP, the first ligandsmay be removed without substantially affecting the second ligandsof the PIsthat are the inhibition moieties, and the PIsmay chemically bond with the base layer. For example, when the first ligandis a methoxy (—OCH) ligand, the methyl group may be removed when HO is supplied, and the first ligandmay chemically bond with the base layer. After the methyl group is removed from the PIs, a moiety that does not chemically bond with the base layermay be OH-terminated.

3 3 FIGS.E andF 350 350 350 200 360 350 200 360 350 320 350 200 360 Referring totogether, some of the PIsare removed. In some example embodiments, some of the PIsmay be removed through Atomic Layer Etching (ALE). For example, some of the PIs, which are not positioned between the upper surface of the base layerand the lower surface of the side surface spacer layer—that is, the PIsattached to a portion of the upper surface of the base layerwhere the side surface spacer layeris not located and the PIsattached to the surface of the mandrel hard mask patternP—may be removed, while the PIspositioned between the upper surface of the base layerand the lower surface of the side surface spacer layermay remain.

3 3 FIGS.F andG 350 200 360 350 360 350 360 350 200 360 200 360 350 360 200 300 310 300 360 350 350 360 360 360 350 360 360 360 2 2 2 Referring totogether, the PIsarranged between the upper surface of the base layerand the lower surface of the side surface spacer layermay be converted into a spacer bonding layerL, thus forming a plurality of spacer patternsA each having a stack structure including the spacer bonding layerL and the side surface spacer layer. The spacer bonding layerL may be arranged between the upper surface of the base layerand the lower surface of the side surface spacer layer, thus bonding the base layerto the side surface spacer layer. The spacer bonding layerL may be a monolayer. The spacer patternsA may cover portions of the upper surface of the base layer, which are adjacent to the mandrel patternsP, and the side surfaces of the mandrel base patternP of each mandrel patternP. When the central elements of the material forming the side surface spacer layerare the same as those of the PIs, the spacer bonding layerL of the spacer patternA may be formed integrally with the side surface spacer layer. In other words. The spacer patternA may be an integral structure of the spacer bonding layerL and the side surface spacer layer. The spacer patternA may include metal oxide. For example, the spacer patternA may include TiO, HfO, or ZrO.

356 350 350 200 300 360 350 350 3 2 2 2 2 In some example embodiments, the second ligandsof the PIsare removed through treatment using oxygen (O) radicals, and thus, the PIs may be converted into the spacer bonding layerL. For example, by supplying ozone (O) or plasma that includes oxygen radicals (O, HO, NO, CO, or NO) on the base layeron which the mandrel patternsP and the side surface spacer layersare formed, the PIsmay be converted into the spacer bonding layerL.

3 3 FIGS.G andH 310 320 320 Referring totogether, the upper surfaces of the mandrel base patternsP are exposed by removing the mandrel hard mask patternsP. The mandrel hard mask patternsP may be removed through etching.

3 3 FIGS.H andI 310 360 200 310 Referring totogether, the mandrel base patternsP are removed, leaving the spacer patternsA on the base layer. The mandrel base patternsP may be removed by ashing and/or stripping.

3 3 FIGS.I andJ 200 360 200 200 Referring totogether, the base layeris patterned using the spacer patternsA as etch masks, and thus, the base patternsP are formed. The base patternsP may be referred to as hard mask patterns.

3 3 FIGS.J andK 110 200 110 110 110 Referring totogether, the target layeris patterned using the base patternsP as etch masks, thereby forming a plurality of target patternsP. For example, the target patternsP may be a plurality of active regions or a plurality of conductive line patterns. In some example embodiments, the target patternsP may define a plurality of hole patterns.

3 3 FIGS.A toK 200 110 360 310 Referring totogether, the base patternsP and the target patternsP may be patterned using the spacer patternsA formed to cover the side surfaces of the mandrel base patternsP.

200 200 300 300 300 300 200 200 200 200 For example, when spacer patterns are formed on the base layerby first forming a spacer layer, which conformally covers the base layerand the mandrel patternsP, and then anisotropically etching the spacer layer and removing the mandrel patternsP, the spaces between the spacer patterns may be formed to have depths that are different from the depths of the spaces where the mandrel patternsP were located and the depths of the spaces where the mandrel patternsP were not located. Therefore, when the base patternsP are formed by patterning the base layerby using the spacer patterns as etch masks, defects may occur, wherein the defects include a decrease in the uniformity of the base patternsP or the collapse of some of the base patternsP.

360 310 360 300 200 110 360 However, because the spacer patternsA are formed to cover only the side surfaces of the mandrel base patternsP, the spaces between the spacer patternsA may be formed to have depths that are the same as or substantially similar to each other, regardless of whether the mandrel patternsP are present. Therefore, the base patternsP and the target patternsP, which are patterned using the spacer patternsA, may have improved uniformity.

4 4 FIGS.A andB are cross-sectional views illustrating a method of manufacturing an integrated circuit device, according to an example embodiment.

3 4 FIGS.F andA 310 320 320 Referring totogether, the upper surfaces of the mandrel base patternsP are exposed by removing the mandrel hard mask patternsP. The mandrel hard mask patternsP may be removed through etching.

4 4 FIGS.A andB 3 3 FIGS.J andK 350 200 360 350 360 350 360 350 350 350 350 310 360 200 200 110 Referring totogether, the PIs, which are arranged between the upper surface of the base layerand the lower surface of the side surface spacer layer, may be changed to the spacer bonding layerL, thereby forming the spacer patternsA each having a stack structure of the spacer bonding layerL and the side surface spacer layer. For example, the PIsmay be changed to the spacer bonding layerL through O radical treatment. During the O radical treatment for converting the PIsinto the spacer bonding layerL, the mandrel base patternsP are removed as well such that the spacer patternsA may remain on the base layer. Then, referring totogether, the base patternsP and the target patternsP may be formed.

5 5 FIGS.A toF 5 5 FIGS.A toF 3 FIG.C 3 FIG.D 3 FIG.G 350 360 360 2 are conceptual views for describing a method of manufacturing an integrated circuit device, according to an example embodiment. In detail,illustrate a method of manufacturing an integrated circuit device in a case where the PIofinclude TMPMCT and the side surface spacer layerofand the spacer patternA ofinclude TiO.

5 FIG.A 3 FIG.B 300 310 320 200 200 310 320 200 320 200 320 310 310 Referring totogether with, the plurality of mandrel patternsP, each of which has a stack structure including the mandrel base patternP and the mandrel hard mask patternP, are formed on the base layer. In some example embodiments, the surfaces of the base layer, the mandrel base patternP, and the mandrel hard mask patternP may each be hydrophilic. For example, when the base layerand the mandrel hard mask patternP include Si, each of the base layerand the mandrel hard mask patternP may have an oxygen-terminated surface. For example, when the mandrel base patternP includes C, the mandrel base patternP may have a hydroxy-terminated surface.

5 5 FIGS.A andB 3 FIG.B 310 200 320 310 310 Referring totogether with, the surface of the mandrel base patternP may be reduced to become hydrophobic through H radical treatment. Each of the surface of the base layerand the surface of the mandrel hard mask patternP may remain hydrophilic. For example, when the mandrel base patternP includes C, the mandrel base patternP may have a hydrogen-terminated surface through H radical treatment.

5 FIG.C 3 FIG.C 200 300 350 350 200 320 300 350 200 320 310 Referring totogether with, the surfaces of the base layerand the mandrel patternsP are exposed to the PIs, and thus, the PIsare attached to the surface of the base layerand the surface of the mandrel hard mask patternP of each mandrel patternP. The PImay be attached to the surface of the base layerand the surface of the mandrel hard mask patternP, both of which are hydrophilic, and may not be attached to the surface of the mandrel base patternP that is hydrophobic.

350 350 352 354 352 356 352 352 350 354 356 For example, the PImay be an organo-metallic precursor that includes a moiety capable of suppressing chemical bonding. The PIincludes a central element, a first ligandbonded to the central element, and a second ligand. In some example embodiments, the central elementmay include metal. For example, the central elementmay include Ti. For example, the PIsmay be TMPMCT. The first ligandmay be an alkoxy ligand, and the second ligandmay be a cyclopentadienyl ligand.

200 320 200 320 310 200 320 200 320 200 320 The alkoxy ligands of each TMPMCT may be attached to the surface of the base layerand the surface of the mandrel hard mask patternP. For example, the alkoxy ligands of each TMPMCT may be attached to the surfaces of the base layerand the mandrel hard mask patternP, both of which are hydrophilic, but may not be attached to the surface of the mandrel base patternP, which is hydrophobic. TMPMCTs may be attached to the surfaces of the base layerand the mandrel hard mask patternP as a monolayer. For example, TMPMCT may not adhere to the TMPMCT already attached to the surfaces of the base layerand the mandrel hard mask patternP. In some example embodiments, at least some of the alkoxy ligands of some of TMPMCTs may be converted to OH, and thus, at least some of the TMPMCTs may chemically bond with the base layerand/or the mandrel hard mask patternP.

5 FIG.D 3 FIG.D 2 2 2 200 300 200 300 310 310 200 300 200 320 Referring totogether with, a preprocessing process of flowing HO onto the base layerand the mandrel patternsP may be conducted. When HO is supplied onto the base layerand the mandrel patternsP, the mandrel base patternP may have a hydroxy-terminated surface; thus, the surface of the mandrel base patternP may become hydrophilic. When HO is supplied onto the base layerand the mandrel patternsP, the alkoxy ligands in TMPMCT may be changed to OH. Hereafter, TMPMCT may refer to the state in which the alkoxy ligands are converted to OH and chemically bond with the base layerand the mandrel hard mask patternsP.

5 FIG.E 3 FIG.D 200 300 360 360 360 360 2 4 4 2 2 2 4 3 2 4 2 3 2 2 4 4 2 4 2 4 4 4 Referring totogether with, a spacer deposition precursor DP is injected onto the base layerand the mandrel patternsP, thus forming the side surface spacer layer. In some example embodiments, for example, the side surface spacer layermay include TiO. In some example embodiments, the side surface spacer layermay be formed through ALD using the DP. For example, the DP may include TDMAT, TiCl, titanium tetrakis(isopropoxide) (Ti(O-iPr)), cyclopentadienyl titanium, titanium bis(isopropoxide)bis(2,2,6,6-tetramethyl-3,5-heptanedionate) (Ti(O-iPr)(thd)), tetrakis(diethylamino)titanium (TEMAT, (EtN)Ti), trimethoxy(pentamethylcyclopentadienyl)titanium ((Cp*)Ti(OMe)), or any derivatives thereof, but is not limited thereto. In some example embodiments, when the side surface spacer layerincludes HfO, the DP may include TDMAHf, HfCl, Hf(iPr)(NMe), HfCpMe, Hf(OtBu), Hf(OEt), Hf(NEt), Hf(NMe), Hf(NMeEt), Hf(thd)(where, thd=2,2,6,6,-tetramethyl-3,5-heptanedionate) or any derivatives thereof, but is not limited thereto.

360 310 200 320 360 310 200 320 200 360 The side surface spacer layermay be formed only on the surface of the mandrel base patternP, but may not be formed on the surfaces of the base layerand the mandrel hard mask patternP. For example, the side surface spacer layermay be formed on the surface of the mandrel base patternP, to which TMPMCT does not adhere, but may not be formed on the surfaces of the base layerand the mandrel hard mask patternP where TMPMCT adhere and cyclopentadienyl ligands are exposed. For example, the upper surface of the base layerand the lower surface of the side surface spacer layermay be spaced apart from each other with the cyclopentadienyl ligands therebetween.

2 2 200 300 360 360 5 FIG.D 5 FIG.E In some example embodiments, instead of injecting HO onto the base layerand the mandrel patternsP before the side surface spacer layerofis formed, HO may be injected along with the DP to form the side surface spacer layerof.

2 200 300 310 360 When HO is supplied onto the base layerand the mandrel patternsP, the surface of the mandrel base patternP becomes hydrophilic, and thus, the growth rate of the side surface spacer layermay increase.

5 5 FIGS.E andF 3 FIG.G 200 360 350 360 350 360 350 360 200 300 310 300 360 350 350 360 360 360 350 360 Referring totogether with, TMPMCT between the upper surface of the base layerand the lower surface of the side surface spacer layeris converted into the spacer bonding layerL, thereby forming the spacer patternsA each having a stack structure including the spacer bonding layerL and the side surface spacer layer. The spacer bonding layerL may be a monolayer. The spacer patternsA may cover portions of the upper surface of the base layer, which are adjacent to the mandrel patternsP, and the side surfaces of the mandrel base patternP of each mandrel patternP. When the central elements of the material forming the side surface spacer layerare the same as the central elements of the PIs, such as Ti, the spacer bonding layerL of the spacer patternA may be formed integrally with the side surface spacer layer. In other words, the spacer patternA may be an integral structure of the spacer bonding layerL and the side surface spacer layer.

350 200 300 360 350 3 2 2 2 2 In some example embodiments, the cyclopentadienyl ligands in TMPMCT may be removed through O radical treatment, the TMPMCT may be converted into the spacer bonding layerL. For example, by supplying Oor plasma including O radicals (O, HO, NO, CO, or NO) onto the base layeron which the mandrel patternsP and the side surface spacer layersare formed, TMPMCT may be converted into the spacer bonding layerL.

6 6 FIGS.A andB are cross-sectional views illustrating a method of manufacturing an integrated circuit device, according to an example embodiment.

3 6 FIGS.F andA 350 200 360 350 360 350 360 350 360 200 300 310 300 360 350 360 350 360 350 360 350 360 350 360 2 2 2 2 2 2 2 2 2 2 2 2 Referring totogether, the PIs, which are arranged between the upper surface of the base layerand the lower surface of the side surface spacer layer, may be changed to a spacer bonding layerB, thereby forming a plurality of spacer patternsB each having a stack structure of the spacer bonding layerB and the side surface spacer layer. The spacer bonding layerB may be a monolayer. The spacer patternsB may cover portions of the upper surface of the base layer, which are adjacent to the mandrel patternsP, and the side surfaces of the mandrel base patternP of each mandrel patternP. When the central elements of the material forming the side surface spacer layerare different from those of the PIs, the spacer patternB may have a stack structure including the spacer bonding layerB and the side surface spacer layer. When the spacer bonding layerB includes TiO, the side surface spacer layermay include HfO, ZrO, SiO, or SiN, and when the spacer bonding layerB includes HfO, the side surface spacer layermay include TiO, ZrO, SiO, or SiN, and when the spacer bonding layerB includes ZrO, the side surface spacer layermay include TiO, HfO, SiO, or SiN.

356 350 350 350 200 300 360 350 350 3 2 2 2 2 In some example embodiments, the second ligandsin the PIsmay be removed through O radical treatment, and the PIsmay be converted into the spacer bonding layerB. For example, by supplying Oor plasma including O radicals (O, HO, NO, CO, or NO) onto the base layeron which the mandrel patternsP and the side surface spacer layersare formed, the PIsmay be converted into the spacer bonding layerB.

6 6 FIGS.A andB 3 3 FIGS.J andK 310 320 320 310 360 200 310 200 110 Referring totogether, the upper surfaces of the mandrel base patternsP are exposed by removing the mandrel hard mask patternsP. The mandrel hard mask patternsP may be removed through etching. Then, the mandrel base patternsP are removed, leaving the spacer patternsB on the base layer. The mandrel base patternsP may be removed by ashing and/or stripping. Then, referring totogether, the base patternsP and the target patternsP may be formed.

7 7 FIGS.A toE are cross-sectional views illustrating a method of manufacturing an integrated circuit device, according to an example embodiment.

7 FIG.A 3 3 FIGS.G andH 320 200 310 200 200 310 310 200 310 310 200 200 Referring to, while the mandrel hard mask patternsP ofare removed, upper portions of the base layeron which the mandrel base patternsP are not positioned, are removed. Thus, a plurality of first recessesRA may be formed. The first recessesRA may be alternately formed or not formed in the spaces between two adjacent mandrel base patternsP among the mandrel base patternsP. For example, the first recessRA may be formed under one of the two spaces between three adjacent mandrel base patternsP among the mandrel base patternsP, but may not be formed under the other. The bottom surface of the first recessRA may be at a lower vertical level than the uppermost surface of the base layer.

7 FIG.B 3 3 FIGS.H andI 310 200 310 310 200 200 310 310 200 310 310 200 200 Referring to, while the mandrel base patternsP ofare removed, upper portions of the base layeron the lower portions of the mandrel base patternsP may be removed together with the mandrel base patternsP such that a plurality of second recessesRB may be formed. The second recessesRB may be alternately formed or not formed in the spaces between two adjacent mandrel base patternsP among the mandrel base patternsP. For example, the second recessRB may be formed under one of the two spaces between three adjacent mandrel base patternsP among the mandrel base patternsP, but may not be formed under the other of the two spaces. The bottom surface of the second recessRB may be at a lower vertical level than the uppermost surface of the base layer.

7 FIG.C 3 3 FIGS.G andH 3 3 FIGS.H andI 7 FIG.A 7 FIG.B 320 310 200 200 200 200 200 310 200 310 310 200 200 200 200 Referring to, while the mandrel hard mask patternsP ofand the mandrel base patternsP ofare removed, upper portions of the base layerare removed, and thus, the first recessesRA ofand the second recessesRB ofmay be formed. The first recessesRA and the second recessesRB may be alternately formed in the spaces between the mandrel base patternsP. For example, the first recessRA may be formed under one of two spaces between three adjacent mandrel base patternsP among the mandrel base patternsP, and the second recessRB may be formed under the other of the two spaces. In some example embodiments, the bottom surface of the first recessRA and the bottom surface of the second recessRB may each be at a lower vertical level than the uppermost surface of the base layerbut may be at the same vertical level.

7 FIG.D 3 3 FIGS.G andH 3 3 FIGS.H andI 200 200 320 200 200 310 200 200 310 200 310 310 200 200 200 200 200 200 Referring to, a plurality of first recessesRAa may be formed as upper portions of the base layerare removed during the removal of the mandrel hard mask patternsP shown in, and a plurality of second recessesRBa may be formed as other upper portions of the base layerare removed during the removal of the mandrel base patternsP shown in. The first recessesRAa and the second recessesRBa may be alternately formed in the spaces between the mandrel base patternsP. For example, the first recessRAa may be formed under one of two spaces between three adjacent mandrel base patternsP among the mandrel base patternsP, and the second recessRBa may be formed under the other of the two spaces. In some example embodiments, the bottom surface of the first recessRAa and the bottom surface of the second recessRBa may each be at a lower vertical level than the uppermost surface of the base layer, and the bottom surface of the second recessRBa may be at a lower vertical level than the bottom surface of the first recessRAa.

7 FIG.E 3 3 FIGS.G andH 3 3 FIGS.H andI 200 200 320 200 200 310 200 200 310 200 310 310 200 200 200 200 200 200 Referring to, a plurality of first recessesRAb may be formed as upper portions of the base layerare removed during the removal of the mandrel hard mask patternsP shown in, and a plurality of second recessesRBb may be formed as other upper portions of the base layerare removed during the removal of the mandrel base patternsP shown in. The first recessesRAb and the second recessesRBb may be alternately formed in the spaces between the mandrel base patternsP. For example, the first recessRAb may be formed under one of two spaces between three adjacent mandrel base patternsP among the mandrel base patternsP, and the second recessRBb may be formed under the other of the two spaces. In some example embodiments, the bottom surface of the first recessRAb and the bottom surface of the second recessRBb may each be at a lower vertical level than the uppermost surface of the base layer, and the bottom surface of the first recessRAb may be at a lower vertical level than the bottom surface of the second recessRBb.

7 7 FIGS.A toE 3 FIG.I 3 3 FIGS.G andH 3 3 FIGS.H andI 3 FIG.J 3 FIG.K 360 200 200 200 200 320 200 200 200 200 310 200 110 360 Referring totogether with, the depths of the spaces between the spacer patternsA may be the same as or substantially similar to each other. For example, the first recessesRA,RAa, andRAb, which are formed as upper portions of the base layerare removed during the removal of the mandrel hard mask patternsP shown in, and the second recessesRB,RBa, andRBb, which are formed as other upper portions of the base layerare removed during the removal of the mandrel base patternsP shown in, may be designed to have a relatively small depth difference, and thus, the base patternsP ofand the target patternsP of, which are patterned using the spacer patternsA, may have improved uniformity.

8 FIG. is a flowchart of a method of manufacturing an integrated circuit device, according to an example embodiment.

8 FIG. 210 Referring to, in operation S, an upper base layer and an upper mandrel pattern are sequentially formed on a lower base layer. In some example embodiments, the upper mandrel pattern may be formed to have a stack structure including an upper mandrel base pattern and an upper mandrel hard mask pattern. In some example embodiments, the upper mandrel pattern may be a single layer.

220 120 150 1 FIG. In operation S, after the upper mandrel pattern is formed, upper spacer patterns are formed on side surfaces of the upper mandrel pattern. In some example embodiments, the upper spacer patterns may be formed according to the same method as that used to form the spacer patterns described in operations Sto Sof. In some example embodiments, the upper spacer patterns may be formed by first forming an upper spacer layer, which conformally covers the upper base layer and the upper mandrel pattern, and then anisotropically etching the upper spacer layer.

230 240 In operation S, the upper mandrel pattern is removed, leaving the upper spacer patterns on the upper base layer. Then, in operation S, the upper base layer is patterned using the upper spacer pattern as an etch mask, thus forming a lower mandrel pattern. The lower mandrel pattern may be formed to have a stack structure including a lower mandrel base pattern and a lower mandrel hard mask pattern.

250 120 150 1 FIG. In operation S, after the lower mandrel pattern is formed, a lower spacer pattern is formed on side surfaces of the lower mandrel pattern. For example, the lower spacer pattern may be formed according to the same method as that used to form the spacer pattern described in operations Sto Sof.

260 270 In operation S, the lower mandrel pattern is removed, leaving the lower spacer pattern on the lower base layer. In operation S, the lower base layer is patterned using the lower spacer pattern as an etch mask, thus forming a base pattern. In some example embodiments, a target layer located on the lower portion of the base pattern may be patterned using the base pattern as an etch mask, thus forming a target pattern.

9 9 FIGS.A toH are cross-sectional views illustrating a method of manufacturing an integrated circuit device, according to an example embodiment.

9 FIG.A 3 FIG.A 3 FIG.A 110 200 300 400 100 200 200 300 300 200 300 Referring to, a target layer, a lower base layer, an upper base layer, and a plurality of upper mandrel patternsP are sequentially formed on a substrate. The lower base layermay be the same as or substantially similar to the base layershown in, and the upper base layermay be the same as substantially similar to the preliminary mandrel layershown in. The lower base layermay be referred to as a base layer, and the upper base layermay be referred to as a preliminary mandrel layer.

300 310 320 320 310 310 200 310 310 320 310 320 310 320 200 320 2 The upper base layermay have a stack structure including a first upper base layerand a second upper base layer. The second upper base layermay have a thickness less than that of the first upper base layer. The first upper base layermay include a material having etch selectivity relative to the lower base layer. For example, the first upper base layermay include a material containing C. The first upper base layerand the second upper base layermay include different materials. For example, the first upper base layermay include C, and the second upper base layermay not include C. In some example embodiments, the first upper base layermay include an ACL or a C-SOH. In some example embodiments, the second upper base layermay include the same material as the lower base layer. For example, the second upper base layermay include an insulating material such as SiON or SiO.

400 410 420 420 410 410 320 410 420 410 420 410 420 320 420 400 p 2 Each of the upper mandrel patternsP may be formed to have a stack structure including an upper mandrel base patternP and an upper mandrel hard mask patternP. The upper mandrel hard mask patternP may have a thickness less than that of the upper mandrel base patternP. The upper mandrel base patternP may include a material having etch selectivity relative to the second upper base layer. The upper mandrel base patternP and the upper mandrel hard mask patternmay include different materials. For example, the upper mandrel base patternP may include C, and the upper mandrel hard mask patternP may not include C. In some example embodiments, the upper mandrel base patternP may include an ACL or a C-SOH. In some example embodiments, the upper mandrel hard mask patternP may include the same material as the second upper base layer. For example, the upper mandrel hard mask patternmay include an insulating material such as SiON or SiO, and in some example embodiments, the upper mandrel patternP may be formed through EUV lithography.

9 FIG.B 460 400 460 300 400 410 400 460 2 2 2 2 Referring to, a plurality of upper spacer patternsA are formed on both side surfaces of the upper mandrel patternsP. For example, the upper spacer patternsA may cover portions of the upper surface of the upper base layer, which are adjacent to the upper mandrel patternsP, and side surfaces of the upper mandrel base patternP of each upper mandrel patternP. The upper spacer patternA may include TiO, HfO, ZrO, SiO, or SiN.

9 9 FIGS.B andC 3 3 FIG.G toI 3 4 4 FIGS.F,A, andB 3 3 FIGS.C toI 4 4 FIGS.A andB 6 6 FIGS.A andB 400 460 300 400 300 300 460 360 360 360 Referring to, the upper mandrel patternsP are removed, leaving the upper spacer patternsA on the upper base layer. The upper mandrel patternsP may be removed according to the same method as that used to remove the mandrel patternsP ofor the mandrel patternsP of. The upper spacer patternsA may be formed according to the same method as that used to form the spacer patternsA of, the spacer patternsA of, or the spacer patternsB of.

9 9 FIGS.C andD 300 300 460 300 310 310 320 320 Referring to, a plurality of lower mandrel patternsP are formed by patterning the upper base layerby using the upper spacer patternsA as etch masks. The lower mandrel patternsP may each be formed to have a stack structure that includes the mandrel base patternP, which is a portion of the first upper base layer, and the mandrel hard mask patternP, which is a portion of the second upper base layer.

9 FIG.E 360 300 360 200 300 310 300 360 2 2 2 2 Referring to, the lower spacer patternsA are formed on both side surfaces of the lower mandrel patternsP. For example, the lower spacer patternsA may cover portions of the upper surface of the lower base layer, which are adjacent to the lower mandrel patternsP, and the side surfaces of the mandrel base patternP of each lower mandrel patternP. The lower spacer patternA may include TiO, HfO, ZrO, SiO, or SiN.

9 9 FIGS.E andF 3 3 FIG.G toI 3 4 4 FIGS.F,A, andB 3 3 FIGS.C toI 4 4 FIGS.A andB 6 6 FIGS.A andB 300 360 200 300 300 300 360 360 360 360 Referring totogether, the lower mandrel patternsP are removed, leaving the lower spacer patternsA on the lower base layer. The lower mandrel patternsP may be removed according to the same method as that used to remove the mandrel patternsP ofor the mandrel patternsP of. The lower spacer patternsA may be formed according to the same method as that used to form the spacer patternsA of, the spacer patternsA of, or the spacer patternsB of.

9 9 FIGS.F andG 200 360 200 200 Referring totogether, the lower base layeris patterned using the lower spacer patternsA as etch masks, and thus, the base patternsP are formed. The base patternsP may be referred to as a plurality of hard mask patterns.

9 9 FIGS.G andH 110 200 110 110 110 Referring totogether, the target layeris patterned using the base patternsP as etch masks, thereby forming a plurality of target patternsP. For example, the target patternsP may be a plurality of active regions or a plurality of conductive line patterns. In some example embodiments, the target patternsP may define a plurality of hole patterns.

10 10 FIGS.A toD are cross-sectional views illustrating a method of manufacturing an integrated circuit device, according to an example embodiment.

10 FIG.A 110 200 300 400 100 460 300 400 400 400 320 400 400 400 460 400 460 460 2 Referring to, a target layer, a lower base layer, an upper base layer, and a plurality of upper mandrel patternsPA are sequentially formed on a substrate, and then, an upper spacer layerP conformally covering the upper base layerand the upper mandrel patternsPA is formed. In some example embodiments, each of the upper mandrel patternsPA may be a single layer. The upper mandrel patternPA may include a material having etch selectivity relative to the second upper base layer. The upper mandrel patternPA may include C. For example, the upper mandrel patternPA may include an ACL or a C-SOH. In some example embodiments, the upper mandrel patternPA may be formed through EUV lithography. The upper spacer layerP may include a material having etch selectivity relative to the upper mandrel patternPA. For example, the upper spacer layerP may include an insulating material that does not contain C. In some example embodiments, the upper spacer layerP may include SiO, metal oxide, or SiN.

10 10 FIGS.A andB 460 460 460 400 Referring totogether, a plurality of upper spacer patternsB are formed by anisotropically etching the upper spacer layerP. The upper spacer patternsB may be formed to cover the side surfaces of the upper mandrel patternsPA.

10 10 FIGS.B andC 400 460 300 Referring totogether, the upper mandrel patternsPA are removed, leaving the upper spacer patternsB on the upper base layer.

10 10 FIGS.C andD 9 9 FIGS.E andH 300 300 460 300 310 310 320 320 200 110 Referring totogether, the lower mandrel patternsP are formed by patterning the upper base layerby using the upper spacer patternsB as etch masks. The lower mandrel patternsP may each be formed to have a stack structure that includes the mandrel base patternP, which is a portion of the first upper base layer, and the mandrel hard mask patternP, which is a portion of the second upper base layer. Then, referring totogether, the base patternsP and the target patternsP may be formed.

While the inventive concepts has been particularly shown and described with reference to some example embodiments thereof, it will be understood that various changes in form and details may be made therein without departing from the spirit and scope of the following claims.